Composite article containing high purity hot pressed boron nitride

ABSTRACT

High purity boron nitride articles of manufacture having a high density and improved properties. The improved boron nitride articles have a unique acicular crystal structure, an oxygen content of less than 0.5 per cent by weight, a density of at least 1.9 grams/cc., excellent hot strength, low coefficients of thermal expansion with no irreversible thermal expansion, excellent thermal shock resistance, moisture insensitivity and improved dielectric properties. These articles are produced by treating conventional hot pressed boron nitride articles with a suitable solvent to lower their boron oxide (B2O3) content, and then sintering the treated material in an inert atmosphere at a temperature of from 1,600* to 2,100* C. in the absence of pressure or mechanical restraint. If it is desired to render these articles electrically conductive, an electrically conductive refractory compound may be incorporated therein. Composite articles produced in this manner can be used to produce resistance heated evaporating crucibles for the vaporization of metals.

United States Patent Mandorf, Jr. et al.

[ June 27, 1972 COMPOSITE ARTICLE CONTAINING HIGH PURITY HOT PRESSED BORON NITRIDE Primary Examiner-Douglas J. Drummond Att0rneyPaul A. Rose, Robert C. Cummings and John S. Piscitello [57] ABSTRACT High purity boron nitride articles of manufacture having a high density and improved properties. The improved boron nitride articles have a unique acicular crystal structure, an oxygen content of less than 0.5 per cent by weight, a density of at least 1.9 grams/cc., excellent hot strength, low coefficients of thermal expansion with no irreversible thermal expansion, excellent thermal shock resistance, moisture insensitivity and improved dielectric properties. These articles are produced by treating conventional hot pressed boron nitride articles with a suitable solvent to lower .their boron oxide (B 0 content, and then sintering the treated material in an inert atmosphere at a temperature of from 1,600 to 2,l00 C. in the absence of pressure or mechanical restraint. If it is desired to render these articles electrically conductive, an electrically conductive refractory compound may be incorporated therein. Commetals.

I 12 Claims, 2 Drawing Figures COMPOSITE ARTICLE CONTAINING HIGI-I PURITY I-IOT PRESSED BORON NITRIDE CROSS-REFERENCE TO RELATED APPLICATIONS I This application is a continuation-in-part application of application, Ser. No. 822,214, filed May 6, 1969 now abandoned.

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to high purity boron nitride articles. More particularly this invention relates to high purity hot pressed boron nitride articles of manufacture having a high density and improved properties.

2. Description of the Prior Art Boron nitride articles are generally fabricated by pressmolding and sintering techniques. The techniques employed are broadly classified as:

a. The hot pressing method: wherein sintering (at l,700 to 2,200 C.) is carried out simultaneously with the pressure molding process.

b. The cold pressing method: wherein press molding is first carried out, and then sintering is carried out.

A modification of the cold pressing method if disclosed in United Kingdom Pat. specification No. 1,073,936 whereby cold pressed boron nitride powder is sintered by heating in a mold without the application of pressure but while free expansion of the boron nitride due to heating is restricted by the mold.

Boron nitride articles produced by the hot pressing method of fabrication have a high boron oxide (B content. While this material acts as a binder-lubricant during hot-pressing and allows such articles to be hot pressed from boron nitride, it also causes a weakening of the properties of the hot pressed articles. Thus, because of the presence of this material, hot pressed boron nitride articles are weak at high temperatures (flexural strengths of about 3,000 psi. or lower at l,O00 C.), exhibit a permanent expansion upon heating to 1,800 C. and cooling to room temperature of close to one per cent (1 percent) or more, and pick up sufficient moisture (which chemically combines with the boron oxide present to produce boric acid) under normal humidity conditions to cause cracking if the boron nitride is exposed to a rapid rise in temperature. These properties have restricted the use of boron nitride produced in this manner in many high temperature applications where a strong material with reversible thermal expansion and high thermal shock resistance is required.

Boron nitride articles produced by the cold pressing method are of low density (about 1.5 grams/cc. to 1.6 grams/cc.) and low flexural strength (about 3,000 psi. from room temperature to 1,000 C.). During the sintering stage the cold pressed material undergoes a thermal expansion which remains even after the product is cooled to room temperature. This permanent expansion is caused by the presence of boron oxide (B 0 and is of the order of 4.5 to 5 per cent when sintering temperatures of 1,500 to 2,100" C. are employed. Further, because of the expulsion of boron oxide (B 0 during sintering, it has not been possible to produce cold pressed articles greater than one-fourth inch to one-half inch in thickness (smallest dimension) without cracking them.

While United Kingdom Pat. specification No. 1,073,936 attempts to overcome the irreversible thermal expansion which cold pressed boron nitride undergoes when it is heated to sintering temperatures (and thereby increase its density) by conducting this operation while restricting the free expansion of the boron nitride in a mold, this method has only been successful in raising the bulk specific gravity of such materials from 6 to 9 per cent to as high as 1.705. Furthermore, the pressure exerted by the escape of boron oxide (B 0 during sintering is usually sufficiently great to crack the mold as well as the boron nitride piece itself. In addition, this method does not produce any significant increase in flexural strength over that of conventional cold pressed boron nitride.

United Kingdom Patent specification No. 777,000 reports that hot pressed boron nitride articles having an apparent density in excess of 1.9 grams/cc. can be produced by hot pressing boron nitride particles which had previously been heated in an ammonia atmosphere to reduce the boron oxide content (B 0 Boron nitride articles produced in this manner are reported as having a free boron oxide (B 0 content of as low as 1.67 percent. Attempts by the patentees to lower the boron oxide (B 0 content of such hot pressed articles by heating to 2,l00 C. without the application of pressure resulted in rupturing of the bodies. This rupture was attributed by the patentees to the failure to confine the body in a mold while heating. This experiment demonstrates that boron nitride articles hot pressed from boron nitride which has been treated to reduce its boron oxide (B 0 content prior to hot pressing still rupture upon heating to high temperatures and are unsuitable for high temperature uses.

Pyrolytic boron nitride having a density in excess of 1.90 grams/cc. has been produced by the reaction of boron trichloride and nitrogen. However, this method has been unsuccessful in producing articles greater than one-fourth inch to one-half inch in thickness (smallest dimension.) Furthermore, the properties of this material are extremely anisotropic in nature. Thus, for example, this material has a flexural strength of about 15,000 psi. at room temperature perpendicular to the direction of the layer planes but below 2,500 psi. parallel to the layer planes. The coefiicient of thermal expansion parallel to the direction of the layer planes is about 1 X l0-/ C. to l,800 C. compared to about 25 X 10 C. to 1,800 C. perpendicular to the layer planes.

SUMMARY OF THE INVENTION In accordance with the instant invention it has now been discovered that very high purity boron nitride articles having a high density and a unique acicular crystal structure can be obtained by treating hot pressed boron nitride articles with a suitable solvent to lower their boron oxide (B 0 content and then sintering the treated material in an inert atmosphere at a temperature of from l,800 to 2,l00 C. in the absence of pressure or mechanical restraint. Because of the manner in which these articles are prepared, it is for the first time possible to prepare large structural shapes of boron nitride (e.g., having a thickness [smallest dimension] in excess of 1 inch) having a very low boron oxide (B 0 content and high density. These shapes are characterized by a unique combination of properties riot hitherto found in any available form of boron nitride including excellent hot strength, low coefficients of thermal expansion with no irreversible thermal expansion, excellent thermal shock resistance, moisture insensitivity and improved dielectric properties.

The improved boron nitride articles of the instant invention have an oxygen content of less than 0.5 per cent by weight, generally from 0.1 per cent by weight to 0.2 per cent by weight, and a density of at least 1.9 grams/00., generally from 1.9 grams/cc. to 2.1 grams/cc. While conventional hot pressed boron nitride is characterized by a decrease in flexural strength as it is heated to temperatures up to about 900 C., the hot pressed boron nitride of the instant invention is characterized by an uninterrupted increase in flexural strength with increasing temperatures up to about 2,000 C. The decrease in flexural strength of conventional hot pressed boron nitride up to temperatures of about 900 C. is caused by the presence of relatively large amounts of boron oxide (B 0 which melts at 525 C. and weakens the bonds of the hot pressed article causing a sharp drop in flexural strength of from up to about 15,000 psi. at room temperature to about 3,000 psi. or less at 900 C. Cold pressed boron nitride, on the other hand, has a lower boron oxide (B 0 content and its flexural strength remains constant at about 3,000 psi. when heated from room temperature to 1,000 C. The low flexural strength of this material is attributed to its low density. By contrast, hot pressed boron nitride treated according to the instant invention increases in flexural strength from about 6,000 psi. at room temperature to as high as 17,000 psi. or more at 2,000 C. At 1.000 C., the flexural strength of this material is greater than about 6,000 psi. vs. about 3,000 psi. or less for both conventional hot pressed and cold pressed boron nitride. At 2,000 C., the flexural strength of the treated hot pressed boron nitride increases to as high as 17,000 psi. or more vs. about 8,000 for the untreated hot pressed boron nitride.

Because of the elimination of boron oxide (B the treated hot pressed boron nitride articles of the instant invention undergo no measurable irreversible thermal expansion when heated to 1,800 C. and subsequently cooled to room temperature. By way of contrast, conventional hot pressed boron nitride articles undergo a permanent expansion of close to one per cent (1 percent) or more under these conditions. The absence of irreversible thermal expansion of the hot pressed boron nitride articles of the instant invention and their low thermal expansion characteristics (coefficient of thermal expansion: parallel to the direction of hot pressing, below 2 X 10 C. to l,800 C.; perpendicular to the direction of hot. pressing, below 3 X l0"/ C. to l,800 C. vs. greater than 4 X 10' C. to l,800 C. and 8 X l0 C. to 1,800" C., respectively, for conventional hot pressed boron nitride) 'makes these materials extremely resistant to thermal shock and suitable for use at very high temperatures. While pyrolytic boron nitride also exhibits no irreversible thermal expansion after heating to 1,800 C. and a coefficient of thermal expansion in the direction parallel to the layer planes of about 1 X l0'/C. to 1,800 C., this material is extremely anisotropic in character and its coefficient of thermal expansion in the direction perpendicular to the layer planes is about 25 X 10 C. to 1,800 C.

The elimination of boron oxide (B 0 from the treated boron nitride articles of the instant invention renders these materials extremely non-hygroscopic. As a result they pick up w less than one per cent (1 percent) by weight moisture when exposed to one hundred per cent (100 percent) relative humidity for one hundred (100) hours at room temperature. Thus, after exposure to the aforesaidconditions, the moisture content of such articles has been measured as about 0.8 0.9 per cent by weight. After standing for 72 hours at room temperature at 37 to 45 per cent relative humidity, the moisture content drops to about 0.2 per cent by weight. Conventional cold pressed boron nitride exhibits similar moisture insensitivity, but when conventional hot pressed boron nitride is treated under the same conditions, it picks up in excess of 2 per cent by weight moisture at 100 per cent relative humidity and still possesses at least about 0.5 per cent by weight moisture content after standing for 72 hours at room temperature at 37 to 45 per cent relative humidity. While the boron nitride of the instant invention completely loses absorbed water on heating, the moisture absorbed by conventional hot pressed boron nitride chemically combines with the boron oxide (B 0 present in this material to form boric acid which on heating causes spalling of the hot pressed boron nitride by the rapid expulsion of water at critical temperatures'up to about 300 C.

The improved dielectric properties of the boron nitride articles of the instant invention are also attributed to the low boron oxide (B 0 content of these materials. Typically these materials are characterized by a loss tangent of less than 0.0006 up to 1000 C. and less than 0.005 up to 1400 C. as compared to, for example, loss tangents of more than 0.003 at l,000 C. and more than 0.010 at 1,400 C. for conventional hot pressed boron nitride at 4.44 to 4.53 Gl-Iz (l0 cycles/second). At the latter temperature, the improved boron nitride articles of the instant invention exhibit an increase of less than five per cent percent) in dielectric constant (4.24 at 1,470 C. vs. 4.08 at 25 C.). Further, because of the moisture insensitivity of the boron nitride articles of the instant invention, the electronic properties of these materials are substantially unaffected after long exposure to the atmosphere. On the other hand, moisture absorption greatly in,-

terferes with the dielectric properties of conventional hot pressed boron nitride causing unpredictable variations in loss tangent and reducing the attractiveness of this material for electronic applications, particularly at high temperatures. Dielectric properties of a specimen of boron nitride prepared in accordance with the instant invention are set forth in Table 1 below.

TABLE I Dielectric Properties K Tan A (Dielectric (Dissipation TC Constant) Factor) At 8.52 GHz 25 4.04 0.00025 At 4.44 to 4.53 GHz The high purity hot pressed boron nitride of the instant invention like conventional boron nitride, whether hot pressed, cold pressed or pyrolytic, can be widely utilized because of its excellent combination of properties such as high thermal conductivity, chemical resistance, high electrical resistivity, machinability, nontoxicity and inability to be wet by many molten metals and halide salts. In addition, this novel material can be prepared in structural shapes of a size not possible from cold pressed or pyrolytic boron nitride. Furthermore, because of its low dissipation factor over a wide temperature range this material is well suited for use as microwave and radar dielectric components (radar windows) whereas high loss factors present a serious problem when conventional hot pressed boron nitride is used as the dielectric. In addition, its increased moisture insensitivity, high temperature stability and excellent thermal shock resistance render it useful as plasma arc insulation.

BRIEF DESCRIPTION OF THE DRAWING FIG. 1 is a photornicrograph having a magnification factor of 500 of the surface of a sample of boron nitride which had been hot pressed at a temperature of 1,800 C. under a pressure of 2,000 psi. and then soaked in methanol to remove boron oxide (B 0 and dried. The view is parallel to the direction of hot pressing.

FIG. 2 is a photornicrograph having a magnification factor of 500 of the surface of a sample of boron nitride which had been hot pressed at a temperature of l,800 C. under a pressure of 2,000 psi., soaked in methanol to remove boron oxide (B 0 dried, and then sintered at 2,000 C. by the process of the instant invention. The view, as in FIG. I, is parallel to the acicular compared to the more plate-like structure of FIG. I.

DESCRIPTION OF THE PREFERRED EMBODIMENT The high-purity high density boron nitride articles of the instant invention are produced by first treating conventional hot pressed boron nitride articles to lower their boron oxide (B 0 content, and then sintering the treated material in an inert atmosphere at a temperature of from 1,800 to 2,100 C. in the absence of pressure or mechanical restraint. in order to obtain boron nitride articles having the unique properties described it is necessary to substantially completely remove boron oxide (B 0 from the conventional hot pressed boron nitride article employed before sintering.

Substantially complete removal of boron oxide (B 0 from the conventional hot pressed boron nitride articles employed is effected according to the process of the instant invention by immersing the hot pressed material in a solvent capable of dissolving or reacting with boron oxide (B 0 to form soluble reaction products until it undergoes no further weight loss. The time required to effect removal of boron oxide (B 0 will depend upon the size of the boron nitride piece and the particular solvent employed. When methanol is employed as solvent, leaching for four (4) days has been found necessary for boron nitride cylinders one-half inch (one-half inch) in diameter, eighteen (18) days for cylinders one inch (1 inch) in diameter, and forty-four (44) days for cylinders two and onehalf inches (2% inch) in diameter. With agitation of the methanol solvent, these times can be lowered to one (1) day for boron nitride cylinders one-half inch (86 inch) in diameter, four (4) days for cylinders one inch (1 inch) in diameter, and twenty days for cylinders two and one-half inches (2% inch) in diameter.

Among the solvents which can be employed to effect removal of boron oxide (B 0 are water and alcohols, including primary, secondary and tertiary alcohols. The most preferred alcohols those alcohols containing up to about four (4) carbon atoms. illustrative of the alcohols which can be employed are aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, heptanol, octanol, glycerol, and the like, and aromatic alcohols such as benzyl a1- cohol, phenethyl alcohol and the like. When water is employed as solvent, the boron nitride piece should not exceed one-half inch (56 inch) in diameter in order to effect a complete removal of boron oxide (B 0 The addition of a small amount of a strong acid such as hydrochloric acid to the water helps speed up the dissolution of the boron oxide 2 3)- After immersion in a suitable solvent, the hot pressed boron nitride is first dried by heating and then further heated in the absence of pressure or mechanical restraint in an inert atmosphere at a sintering temperature in the range of from 1,800 to 2,100 C. By an inert atmosphere is meant an atmosphere which is nonreactive with boron nitride under the heating conditions employed. Inert gases such as nitrogen, helium, neon, argon, krypton, xenon, ammonia, and the like, provide suitable atmospheres in which hot pressed boron nitride may be sintered. Temperatures of from l,950 to 2,050 C. are preferred as the highest flexural strengths are obtained at such temperatures. The sintering temperature should not be permitted to exceed 2,100 C. as decomposition of the boron nitride occurs above such temperature. Where lower flexural strengths are tolerable, e.g., about 3,500 psi. at room temperature (perpendicular to pressing direction), sintering temperatures as low as l,600 C. can be employed. Sintering should be continued for about at least 1 hour, preferably at least 2 hours, to obtain the highest flexural strengths.

The following example is set forth for purposes of illustration so that those skilled in the art may better understand this invention and it should be understood that it is not to be construed as limiting this invention in any manner.

15 EXAMPLE 1 A cylindrical boron nitride plug 14 inches long and 14 inches in diameter which had been hot pressed at a temperature of 1,800 C. under a pressure of 2,000 psi. was machined to produce a number of smaller boron nitride pieces, including one 3 X 2 X 0.5 inch in size. This piece was dried by heating at 200 C., weighed, and then immersed in flowing water until no further loss in weight occurred. A period of 14 days was required to bringthe boron nitride piece to constant weight.

25 During this time the piece was periodically removed from the water, dried at 200 C. and weighed to determine if any further loss in weight had occurred. The loss in weight was due to the removal of boron oxide (B 0 and amounted to 5.2 per cent of the original weight of the piece. The flexural strength of the piece after being brought to constant weight was 950 psi. at room temperature (perpendicular to pressing direction).

After the boron nitride piece had been brought to constant weight, it was heated to 2,000 C. under an atmosphere of flowing argon over a period of 4% hours (3 hours to heat from room temperature to l,500 C., 1% hours to heat from 1,500 to 2,000 C.) and maintained at this temperature for 2 additional hours. At the end of this time the piece was weighed again and found to have undergone a further weight loss of 0.85 per cent.

A cylindrical piece of boron nitride 6 inches long and 2% inches in diameter which had been hot pressed at a temperature of 1,800 C. under a pressure of 2,000 psi was sintered as described above after having been immersed in methanol for 44 days to bring it to constant weight. The loss in weight in methanol amounted to 3.3 per cent while the loss in weight during sintering amounted to 0.47 per cent. The flexural strength of the piece after being brought to constant weight in methanol but before sintering was 980 psi. at room temperature (perpendicular to pressing direction).

The properties of the two sintered boron nitride pieces are set forth in Table 11 below and compared to the properties of a like hot pressed boron nitride piece which had not been treated with water or alcohol and sintered at 2000 C., an untreated piece hot-pressed at 2,000" C. and 2,000 psi., a boron nitride piece hot pressed at 1,800 C. and 2,000 psi. from boron nitride containing 1.65 per cent by weight oxygen, a boron nitride piece cold pressed at 30,000 psi. and sintered at 2,000 C., and a piece of pyrolytic boron nitride.

TABLE II BN hot- BN hotpressed at pressed at 1,800 O. and 1,800 C. and EN contain- 2,000 p.s.i., 2,000 p.s.i., ing 1.65% BN coldtreated in treated in BN hot- BN hotoxygen hotpressed at water and methanol and pressed at pressed at pressed at; 30,000 p.s.i. sintered at sintered at 1,800 C. and 2,000 C. and 1,800 C. and and sintered Pyrolytic 2,000 O. 2,000 C. 2,000 p.s.i. 2,000 p.s.i. 2,000 p.s.i. at 2,000 C. BN Oxygen content (wt. percent) 0.3 0.3 2. 9 3.0 1.65 0.3 0 1)o11sity,gr:tms/cc. 1. 9 2.0 2.1 2.1 2. 0 1. 6 2. 2

Floxuml strength, p.s.i.:

Table ll Continued BN hot- BN hotpressed at pressed at 1,800 C. and 1,800 C. and BN contain- 2,000 p.s.i., 2,000 p.s.i., ing 1.65% BN coldtreated in treated in BN hot- BN hotoxygen hotpressed at water and methanol and pressed at pressed at pressed at 30,000 psi. sintered at sinterod at 1,800 C. and 2,000 O. and l,800 C. and and sintered Pyrolytic 2,000 O. 2,000 0. 2,000 psi. 2,000 psi. 2,000 p.s.i. at 2.000 C. BN

0,064 6,000 12,600 I 14, 300 10,900 3,272 15,000 6, 361 7,100 2, 800 2, 500 3, 000 3, 000 17, 000 9, 331 9, 000 2, 800 10.000 2,000 C 14,770 17,000 8,000 37,000 Coeiiicicnt of thermal expanslonXlM/C.

(room temp. to 1,800" 0.):

(A 0.83 0.72 6.5 4.4 1.7 1.0 (11 1.95 9.15 8.3 4.4 1.39 25.0 Percent permanent expansion after heatimz to 1,800" C.:

A 0 1.0 0.7 0.02 0.05 0 (B 0 0 1.5 1 4 0.45 '0 Moisture pickup after exposure to 100% relative humidity for 100 hrs. at room temp, wt. percent 0. 85 0. 9 3. 2. 48 '2. 49 0. 79 0 Moisture content after exposure to 100% relative humidity for 100 hrs. at room temp. and 37-45% relative humidity for 72 his, wt. percent 0. 2 0. 8 "2. 03 90 0. 21 0 140 hours exposure.

140 hours at 100% relative humidity and 16 hours at 3745% relative humidity.

'Piecc cannot be made in suiiicient thickness to measure.

N0'rE.(A) Measured parallel to pressing direction or the direetioNn of pressing direction or across the layer planes in the ease of pyrolytic B mospheric conditions for a week and heated to white heat asthe layer planes in the case of pyrolytic BN; (B) Measured perpendicular to above, i.e., it is first treated with a suitable solvent and then sintcred, after drying, in an inert nonreactive atmosphere at a temperature of from 1,600 to 2,l00 C., preferably from rapidly as possible with an acetylene torch (heating time to l,800 to 2,l00C., in the absence of pressure or mechanical white h ppr y 30 seconds), the surface of the piece restraint. The sintcred composite, like articles fonncd from exploded into Powder and small chunks- The explosion was boron nitride only, is characterized by high density, excellent caused by the expulsion of water resulting from the decomh strength, relatively low ffi i f thermal expansion Position ofbork a p the bm'on nitride" and low irreversible thermal expansion, excellent thermal when a Similar Piece of Pressedboron nitride which had shock resistance, and moisture insensitivity. As in the case of been treated in water and sintered in accordance with the articles f d solely fr boron nitride according to the process of the instant invention was treated in a similar mien, these improved properties are attributed largely to manner by heating three times to white heat and quenching the [ow boron oxide 5 0 Content f h composim twice in cold water no deterioration of the piece occurred. 40 Th boron nitride-refractory compound composites of the n a cylindrical P of boron nm'ide 5 inches long and present invention, like articles formed solely from boron 3% inches in diameter which h been cold pressefi under a nitride according to the invention, have an oxygen content of ffz 't tg 29 5 heated m 39 lcssthan 0.5 per cent by weight. As a result, they are extremee ca 0 re ure er an mos er 8 0 a 36205 -t a .5 2:13;: fairness; malmamed at temperamwfor 2 adfmlonal hours E cent 100 percent) relative humidity for one hundred hours at gzz ggg ztiggm g g g i z zi ggg zfs fg qfil room temperature. Upon heating, this absorbed water is readinitride piece' was removed 'f the i and reheated in 3 1y :71 2:251??? t lfz composites of the present invention vag z g i g g i g so ries with the amount and particular refractory compound em- 5: r jz g r 2 1 1 :1 2 g sgg i ployed. When titanium diboride is the refractory compound, it p g direction, and a flexural strength of 2,500 p at generally varies from 2.6 grams/cc. to 3.4 grams/cc. As in the room temperature perpendicular to the pressing direction. of amcles formefl sole), from boron nimdel the coinlfit is desired to render the g posltes of the present invention are characterized by an unmpurity boron nitride articles t t d fl t t of the instant invention electrically conductive, an electrically e Increase m exura. s {ength mcreasmg em conductive refractory compound may be incorporated perature. Thus, SUCh'CK'MHPQSItCS increase in flexural strength therein. Suitable conductive refractory compounds include (perpendlcular.t the duectlon of hot pressing) from as low as titanium diboride, zirconium diboride, titanium carbide and abfmt 75o0 P at i to at least about IZOOO mixtures thereof. Composites produced in this manner are and as high as 20,090 or more at 1590': usu'fmy electrically conductive and can be used, for example, to from about 13'000 P m about lsooo composfnes produce resistance heated evaporating crucibles for the formed from boron nitride and a refractory compound in a vaporization of metals crucibles of this type are describcdin conventional manner, on the other hand, while exhibiting flexus. Letters Pat. No. 3,181,968 and are used for the dcposi-, strengths as as 30,000 F on f hi metallic films on various Objects. I ture are characterized by a steady decrease in strength at in- The amount f Conductive refractory compound present in creasingl y higher temperatures and have flexural strengths of the composites of the present invention can range from about 3,000 P or less at 15000 50 per cent by weight to about per cent by weight, the When heated to 1,800: C. and subsequently cooled to room balance being boron nitride The boron nitride particles are temperature the composites of the present invention undergo blended with the conductive refractory compound to form a 70 in'evel'sible thermal expansion of less than P cent uniform dispersion of the two materials, and the mixture is hot compared to an irrevel'sibie thermal expansion of greater than pressed at a temperature of from about |,7()() to about 2.000 1.8 per cent which is exhibited by composites formed from C. and n prcssurc of from about 500 to about 2,000 psi. The boron nitride and refracml'y compound in a Conventional rcsulliml hot pressed piece is then treated to lower the boron mmmcrwhile Cmmciem thermal expansion of these oxide (B 0 content and sintered in the manner described comimsiles Wm y depending p the amoum and P lar refractory material present, a 20 per cent to 40 per cent lower coefficient is exhibited by the composites of the present invention, with the coefficient of such composites not exceeding 9.0 X 10'/ C. to l,800 C. (parallel to the direction of hot pressing).

The composites of the present invention exhibit increased thermal shock resistance and can be resistance heated from room temperature to 1,500 C. at a rate of 3,000". C./minute without cracking and are capable of withstanding in excess of 150 such heating cycles without damage from thermal shock. On the other hand, composites formed from boron nitride and a refractory material in a conventional manner crack after only about 20 to 30 such cycles when heated in this manner. Because of the increased thermal shock resistance of the composites of the present invention, resistance heated evaporating crucibles produced from such composites are especially suitable for the flash vaporization of aluminum and other metals in the vacuum metallizing of materials in the electronic and decorative coating industries. In addition, while crucibles produced from boron nitride and a refractory compound in a conventional manner are at the upper limit of their thermal stability at about 1,800 C., crucibles prepared from the composites of the present invention can be employed at temperatures in excess of 2,200" C. Because of this increased thermal stability, the crucibles prepared from the composites of the present invention are especially suitable for the vaporization of metals such as copper, silver, gold, chromium, iron, and the like, where high temperatures are required.

EXAMPLE 2 Fifteen evaporator vessels of the type described in U.S. Letters Pat. No. 3,181,968 were machined from a composite prepared by hot pressing a uniform blend containing 50 per cent by weight titanium diboride and 50 per cent by weight of boron nitride at a temperature of 1,800 C. and a pressure of 2,000 psi. The outside dimensions of each evaporator vessel were 5% inches long by b inch wide by /4 inch thick. The dimensions of the cavity in the vessel were 4 inches long by l 16 inch deep. The vessels had electrical resistivities at room temperature ranging from 927 to 1,266 p. ohm cm. and densities ranging from 2.7 grams/cc. to 2.8 grams/cc.

Each vessel was then dried by heating at 200 C., weighed,

and leached in boiling methanol until no further weight loss 4 occurred. A period of 43 hours was required tobring the vessel to constant weight. The loss in weight was due to the removal of boron oxide (B and averaged 3.5 per cent of the original weight of the vessels.

After leaching, the vessels were dried at 100 C. for 16 hours and then heated to about l,975 C. under an atmosphere of flowing argon over a period of 6 hours (3 hours to heat from room temperature to 1,500 C., 1 hour to heat from 1,500 to l,675 C., 2 hours to heat from 1,675 to l,975 C.) and maintained at this temperature for 3 hours. At the end of this time the vessels were cooled while still in an argon atmosphere. The vessels were then weighed and found to have undergone a further average weight loss of 1.8 per cent (based on the original weight of the vessels). The vessels obtained in this manner had densities ranging from 2.65

grams/cc. to 2.69 grams/cc. and electrical resistivities ranging from 907 to 1,950 pt ohm cm. The average oxygen content of the vessels so treated was determined to be 0.29 per cent by weight, from which a boron oxide (B 0 content of 0.42 per cent was calculated.

EXAMPLE 3 Four evaporator vessels 5 inches long by re inch wide by V;

inch thick having electrical resistivities ranging from 837 to. 1,121 p. ohm cm. at room temperature were prepared in the 0.3 micron of mercury to 1,500 C. in one-half minute, maintaining the temperature at 1,500 C. for one and one-half minutes, and then cooling to below red heat over a period of one and one-half minutes. The power usage during the one and one-half minute hold period was 10 i 0.3 KVA. The vessels each withstood 150 cycles with no sign of cracking. When like hot pressed vessels which were not treated with methanol and sintered at 2,000 C. were tested in a similar manner all failed after only 20 cycles.

The same four evaporator vessels were then each employed in 50 flash aluminum vaporizations. One gram of aluminum was evaporated from each vessel per flash by resistance heating the vessels connected in parallel in the chamber described above to 1,500 C. in one-half minute at a pressure of 0.3 micron of mercury, maintaining the temperature of 1,500 C. for one-half minute, and then cooling to below red heat over a period of one minute. The total power'requirements to flash the aluminum from the vessels atthe flash temperature ranged from 5.1 to 6.3 KVA. After 50 tests, the vessels showed no signs of cracking or failure. On the other hand, hot pressed vessels which have not been treated with methanol and sintered at 2,000 C. fail by cracking after only 4 to 5 cycles.

EXAMPLE 4 An evaporator vessel 5 inches long by inch wide by 1% inch thick (cavity dimensions 3 inches long by Va inch deep) was prepared in the same manner and from the same composition employed in Example 2 and employed in the continuous vaporization of high purity copper. The vessel was placed in a cylindrically shaped vacuum metallizing chamber and resistance heated under a pressure of 0.3 micron of mercury to l,600 C. in two minutes. A roll of 0.064 inch diameter 99 percent plus purity copper was then fed to the vessel cavity at a rate of 5 grams per minute. The rate of feed was maintained during the entire run during which approximately 4.7 pounds of copper were evaporated. The temperature required during this run to maintain copper vaporization was as high as 1,900 C. The vessel operated for 421 minutes without failure.

When a like hot pressed vessel which had not been treated with methanol and sintered at 2,000 C. was employed, the vessel cracked after the introduction of copper to the vessel cavity before it reached the temperature required for EXAMPLE 5 Twenty evaporator vessels of the type described in U.S. Letters Pat. No. 3,181,968 were machined from a composite prepared by hot pressing a'uniform blend containing 70 per cent by weight titanium diboride and 30 per cent by weight of boron nitride at a temperature of l,800 C. and a pressure of 2,000 psi. The outside dimensions of each evaporator vessel were 5 inches long by inch wide by 1% inch thick. The dimensions of the cavity in the vessel were 3 inches long by /s inch deep. The vessels had electrical resistivities at room temperature ranging from 40 to 60 p. ohm cm. and densities ranging from 3.24 grams/cc. to 3.37 grams/cc.

Each vessel was then dried by heating at 200 C., weighed, and leached in boiling methanol until no further weight loss occurred. A period of 12 hours was required to bring the vessel to constant weight. The loss in weight was due to the removal of boron oxide (B 0 and averaged 2.5 per cent of the original weight of the vessels.

After leaching, the vessels were dried at 100 C. for 16 hours and then heated to about l,975 C. under an atmosphere of flowing argon over a period of 6 hours (3 hours to heat from room temperature to 1,500 C., 1 hour to heat from 1,500 to l,675 C., 2 hours to heat from l,675 C. to 1,975" C.) and maintained at this temperature for 3 hours. At the end of this time the vessels were cooled while still in an argon atmosphere. The vessels were then weighed and found to have undergone a further average weight loss of 2.1 per cent (based on the original weight of the vessels). The vessels obtained in this manner had densities ranging from 3.03

grams/cc. to 3.09 grams/cc. and electrical resistivities ranging from 51 to 58 p, ohm cm. The average oxygen content of the vessels so treated was determined to be 0.24 per cent by weight, from which a boron oxide (B content of 0.34 per cent was calculated.

One of the vessels so produced was then employed in the continuous vaporization of high purity copper in the manner described in Example 4. The vessel operated for 87 minutes without failure. When a like hot pressed vessel which had not been treated with methanol and sintered at 2,000 C was employed, the vessel cracked after the introduction of copper to the vessel cavity before it reached the temperature required for vaporization of copper (approximately l,700l,800 C.).

When a similar vessel was prepared in the same manner from the same composition was subjected to the same cyclic thermal shock test as described in Example 3, the vessel withstood 150 cycles with no sign of cracking. When a like hot pressed vessel which had not been treated with methanol and sintered at 2,000 C. was tested in the same manner, it failed after only 30 cycles.

What is claimed is:

1. An electrically conductive composite article consisting essentially of from about 50 per cent by weight to about 70 per cent by weight of an electrically conductive refractory boride compound and from about 30 per cent by weight to about 50 per cent by weight of boron nitride, said composite article having an oxygen content of less than 0.5 per cent by weight, a coefficient of thermal expansion parallel to the direction of hot pressing of below 9.0 l0'/ C. to 1,800 C., an uninterrupted increase in flexural strength-with increasing temperatures up to about l,500 C., a moisture pickup of less than 1 per cent after exposure to 100 per cent relative humidity for 100 hours at room temperature, an irreversible thermal expansion of less than 0.3 per cent when heated to 1,800 C. and subsequently cooled to room temperature, a thermal stability in excess of 2,200 C., and the capacity of being heated in excess of 150 cycles from room temperature to 1,500 C. at a rate of 3,000 C./minute without damage from thermal shock 2. An electrically conductive composite article as in claim 1 wherein the electrically conductive refractory boride compound is titanium diboride.

3. An electrically conductive composite article as in claim 1 in the shape of an evaporating crucible.

4. An electrically conductive composite article as in claim 2 in the shape of an evaporating crucible.

5. A process for producing electrically conductive composite articles having an oxygen content of less than 0.5 per cent by weight which comprises treating a hot pressed blend of from about 50 per cent by weight to about 70 per cent by weight of an electrically conductive refractory boride compound and from about 30 per cent by weight to about 50 per cent by weight of boron nitride with a solvent capable of removing boron oxide therefrom until said hot pressed blend undergoes no further weight loss, drying the hot pressed blend by heating, and sintering the dried treated blend in an inert atmosphere at a temperature of from l,600 to 2,l0O C. in the absence of pressure.

6. A process as in claim 5 wherein the electrically conductive refractory boride compound is titanium diboride.

7. A process as in claim 6 wherein the solvent is selected from the group consisting of water and alcohols.

8. A process as in claim 6 wherein the solvent is methanol.

9. A process as in claim 5 wherein the sintering temperature is from 1,800 to 2,l00 C.

10. A process of claim 9 wherein the electrically conductive refractory boride compound is titanium diboride.

11. A process as in claim 10 wherein the solvent is selected from the group consisting of water and alcohols.

12. A process as in claim 10 wherein the solvent is methanol.

CERTIFICATE OF CORRECTION 3,673,118 June 27, 1972 Patent No. Issue Date Invnmfls) Victor Mandorf, Jr. and Llonel Clayton Montgomery It is certified that error appears in the above-identified patent and that slid Letters Patent are hereby corrected as shown below:

Front page, after "Continuation-in-part of Ser. No. 822,214 May 6, 1969" delete abandoned" Column 1, lines 6-7, delete "now abandoned".

Signed and sealed this 23rd day of January 1973.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents 

2. An electrically conductive composite arTicle as in claim 1 wherein the electrically conductive refractory boride compound is titanium diboride.
 3. An electrically conductive composite article as in claim 1 in the shape of an evaporating crucible.
 4. An electrically conductive composite article as in claim 2 in the shape of an evaporating crucible.
 5. A process for producing electrically conductive composite articles having an oxygen content of less than 0.5 per cent by weight which comprises treating a hot pressed blend of from about 50 per cent by weight to about 70 per cent by weight of an electrically conductive refractory boride compound and from about 30 per cent by weight to about 50 per cent by weight of boron nitride with a solvent capable of removing boron oxide therefrom until said hot pressed blend undergoes no further weight loss, drying the hot pressed blend by heating, and sintering the dried treated blend in an inert atmosphere at a temperature of from 1, 600* to 2,100* C. in the absence of pressure.
 6. A process as in claim 5 wherein the electrically conductive refractory boride compound is titanium diboride.
 7. A process as in claim 6 wherein the solvent is selected from the group consisting of water and alcohols.
 8. A process as in claim 6 wherein the solvent is methanol.
 9. A process as in claim 5 wherein the sintering temperature is from 1,800* to 2,100* C.
 10. A process of claim 9 wherein the electrically conductive refractory boride compound is titanium diboride.
 11. A process as in claim 10 wherein the solvent is selected from the group consisting of water and alcohols.
 12. A process as in claim 10 wherein the solvent is methanol. 